WO2011128073A2 - Utilisation de granulés minéraux naturels comme adsorbeurs de gaz pour l'élimination de composants toxiques gazeux - Google Patents

Utilisation de granulés minéraux naturels comme adsorbeurs de gaz pour l'élimination de composants toxiques gazeux Download PDF

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Publication number
WO2011128073A2
WO2011128073A2 PCT/EP2011/001834 EP2011001834W WO2011128073A2 WO 2011128073 A2 WO2011128073 A2 WO 2011128073A2 EP 2011001834 W EP2011001834 W EP 2011001834W WO 2011128073 A2 WO2011128073 A2 WO 2011128073A2
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WIPO (PCT)
Prior art keywords
gas
mineral
ozone
use according
agglomerate
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Ceased
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PCT/EP2011/001834
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German (de)
English (en)
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WO2011128073A3 (fr
Inventor
Joachim Schomburg
Christian Schultz
Marita Loeffler
Ronny Brandenburg
Volker Brueser
Siegfried Mueller
Katja Saulich
Klaus-Dieter Weltmann
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DURTEC GmbH
Patenthandel Portfoliofonds I & Co KG GmbH
INP Greifswald Leibniz Institut für Plasmaforschung und Technologie eV
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DURTEC GmbH
Patenthandel Portfoliofonds I & Co KG GmbH
INP Greifswald Leibniz Institut für Plasmaforschung und Technologie eV
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Priority to EP11719762A priority Critical patent/EP2558194A2/fr
Publication of WO2011128073A2 publication Critical patent/WO2011128073A2/fr
Publication of WO2011128073A3 publication Critical patent/WO2011128073A3/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/106—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption

Definitions

  • the invention relates to the use of natural mineral granules as Gasadsorber for the removal of gaseous pollutant components such as ozone, siloxanes, formaldehyde, mercaptans, organic amines and hydrocarbons from exhaust air / natural gas or liquids.
  • gaseous pollutant components such as ozone, siloxanes, formaldehyde, mercaptans, organic amines and hydrocarbons.
  • the pollution with these gaseous pollutant components can be in the range of more than 0.1 ppm to 1000 ppm and thus pollute the environment or be harmful to the process.
  • Formaldehyde is often detected as a gaseous pollutant component during heating and combustion processes and as space outgassing when using certain building materials.
  • Siloxanes, formaldehyde, hydrocarbons, organic amines and mercaptans as well as other gaseous sulfur compounds are known in the prior art from the exhaust air and gas streams by means of the synthetically produced molecular sieves, natural zeolites and activated carbon products, which are also possibly modified, used as adsorbents eliminated.
  • WO 2009/125004 describes hailoysites and smectites as novel unmodified gas adsorber granules for the treatment of raw biogas with the aim of removing hydrogen sulfide and ammonia without the possibility of use for fixing siloxanes, hydrocarbons, ozone, organic amines, Formaldehyde and mercaptans is given. Removal of ozone from exhaust air / exhaust gas
  • such a combination is provided with a catalyst which contains a nitrogen compound with nitrogen in a negative oxidation state (ammonia-laden or nitride-containing).
  • the catalyst is cyclically subjected to regeneration.
  • the exhaust air stream is initially passed over an adsorber / catalyst to reduce organic and inorganic pollutants from exhaust gases.
  • the adsorber / catalyst is a solid in the form of granules or chippings with high absorption capacity for the pollutants.
  • the influx of exhaust air is interrupted and the adsorber / catalyst operated in a separate circulatory system - together with a plasma generator - to the degradation of pollutants.
  • the reactive species generated in the plasma are transported via the adsorber / catalyst. lysator thereby degrading the bound pollutants to form water and carbon monoxide.
  • the oxygen necessary for the oxidation is added in the form of air, pure oxygen or ozone.
  • reaction products are part of the circulatory system and ozone is only consumed until the pollutants are degraded.
  • DE 10158970A1 it is provided to produce oxidizing agent with a plasma generator (eg by dielectrically impeded discharge) and to pass it via an adsorbent agent for adsorbing oxidizable substances.
  • the adsorbed substances are oxidatively degraded.
  • a destruction agent is furthermore provided, where the air streams are passed to a destruction agent for catalytic degradation after flowing through the adsorbent.
  • DE 10225492A1 describes the catalytic oxidation of air pollutants with ozone and a cobalt-aluminum mixed oxide.
  • EP 0277843A2 has proposed a zeolite in various configurations as an ozone adsorber.
  • US 2008 / 0017590A1 proposes for industrial processes the use of adsorbers for separating ozone from a gas stream with oxygen, which consist of silica gel, silicon-rich mordenite or Y zeolite.
  • the disadvantage is that these are synthetic mineral products whose production is costly.
  • Also known are special forms of plasma reactors in which pellets with catalytic properties are introduced in the gas space or parts thereof.
  • a system for various pollutants and also for the adsorption of ozone has been put under protection.
  • active materials aluminum, metal oxide catalysts, ferroelectric materials, and ceramic materials are provided.
  • the activated carbon is consumed. Activated carbon is also applicable only at low ozone concentrations, as it may cause inflammation at higher concentrations.
  • the microwave desorption also aims at a corresponding heating of the material.
  • the cost is relatively high, as well as means for shielding are required.
  • Displacement desorption with water vapor also has the disadvantage of increased energy expenditure.
  • the water vapor must also be removed again. It is not known to what extent a similar effect can be achieved with other gases.
  • oxidizable substances VOCs, organic particles
  • oxidants which are used for the regeneration of adsorber materials
  • the oxidizing agents can be generated with the aid of a plasma generator, in particular via a dielectrically impeded discharge. This process, when loaded with pollutants, is virtually an indirect regeneration of the adsorber materials. This only works for oxidizable pollutants and additional a source for the production of a suitable oxidant is required.
  • siloxanes are removed from gas streams using silica gel, zeolites and activated carbon products or by modified mineral gas additives, which are prepared by acid activation or heat treatment in the range from 110 to 1000 ° C., and in the specifications GB 2396315, JP 02083016A, US Pat. JP 2005 040703A and DE 4220950A1, US 2008 179177A, US 2007 0068386 and US 7393381.
  • Hydrophobized silica gel has a 10 times higher loading capacity as activated carbon for siloxanes, but is significantly more expensive than activated carbon products.
  • Jong Kuk Kim et al. "Adsorption of siloxane con- tained in landfill using clay mineral”. - Journ. Korean Indust. and Engin. Chemistry 17 (2006), 465-470 describe a good siloxane adsorption to the four-layer silicate vermiculite (3.8 g / g vermiculite) and recommend this mineral product for the substitution of activated carbon.
  • the desulphurisation of city gas and natural gas aims at target values of ⁇ 5 ppm for sulfur compounds.
  • Synthetic zeolites US Pat. No. 6,579,347, US Pat. No. 3,864,452
  • mixtures of zinc oxide and zeolites US Pat. No. 4,717,552
  • cadmium-exchanged zeolites US Pat. No. 4,358,297
  • activated carbon activated aluminum and silica gel, if appropriate also as mixtures, have proven to be effective adsorber materials (US 7211128, US 7449049, US 4830733).
  • Gas processing for fuel cell technology requires sulfur levels of ⁇ 1 ppm due to the risk of poisoning catalysts contained in the reformers and the fuel cell.
  • activated carbon / zeolites (DE 10347139B4), activated carbon and metal oxides, such as ZnO (DE 10115220A1), zinc oxides (AT 407100B), alumina pellets (US 6294276B1), lead acetate or silver (EP 1926169, EP 2168912) and Sepiolites and / or mi with activated carbon, zeolites, silica gel, diatomaceous earth, which may also be impregnated with metal ions (Co, Mn, Cu, Fe, Cr, Ni) (EP 1501913 Bl) used.
  • biomass bacteria, moss, cellulose, wool
  • formaldehyde CN 101327405, US 6332961.
  • Zeolites e.g. T. also shown from mixtures of hydrophilic and hydrophobized zeolites are described in the patents US 6396823 and CN 101314101. Furthermore, the use of various metal catalysts or platinum or palladium-doped zeolites is prior art (GB 2252968A).
  • a. Exhaust gases used is activated carbon.
  • the US Pat. No. 7,719,957 describes the use of activated carbon in a filter device, which, for. B. can be connected to a Tokar to gases generated during a surgical operation, such as carbon monoxide or gas contamination consisting of smoke u. a. Particles, hydrocarbon vapors u. a. to bind organic odors.
  • adsorbers can be used to first bind organic molecules such as ethers, aldehydes, ketones, alcohols and amines from the vapor phase over an aqueous solution (from fermentation processes).
  • the adsorber used are silicon dioxide, bentonites, silicates, clays, hydrocalcites, aluminum silicates, oxide powders, mica, glass, aluminates, clinoptilolites, gismondines, quartz, activated carbon, bone charcoal, polystyrene, polyurethane, polyacrylamide, polymethacrylate, polyoxygenate 1 p yr i di n and preferably zeolites used.
  • the organic molecules are desorbed by heating and then condensed by cooling.
  • an adsorber which is designed as a hollow fiber after thermal treatment.
  • ceramic materials such as alumina, bentonite, silica, hydroxyapatite or mixtures thereof.
  • VOCs Volatile Organic Compounds
  • Bentonite is also used in column chromatography (microadsorption columns), e.g.
  • a packing material is proposed which has a carrier with a large, inner surface such.
  • B. contains bentonite.
  • WO 2007 060429 a reactor is described in which clays such. As bentonite, used as a slurry dispersed to remove VOC Kontamina- tions from large volumes of air. These favorable properties of the clays are based on complex binding mechanisms, including van der Waals interactions, ligand binding and covalent bonds, and adsorption due to the hydrophobicity of the clays. As a preliminary An organophilization with quaternary ammonium compounds was carried out.
  • EP 414095 a method for exhaust gas removal is presented which u. a. works with an adsorption filter containing as adsorbent both activated carbon, silica gel and bentonite and biomass (peat, compost) as a mixture components.
  • This should be organic pollutants such as hydrocarbons and halogenated HCs such as alkanes, aldehydes, ketones, aromatics, esters, turpentine or alcohols or mixtures of these can be eliminated.
  • DE 69107739 discloses a method of removing hydrocarbon compounds from air and water using bentonite in colloidal form.
  • thermal reactivation processes lead to premature loss of reactivity in multiple treatments as a result of treatment at temperatures> 100 ° C,
  • Adsorbers that work on the basis of biomass mineral mixtures are flammable.
  • the object of the invention is therefore to provide effective and cost-effective ways of treating exhaust gases, exhaust air and pollutant-containing gases.
  • residual ozone, siloxanes, sulfur-containing gaseous compounds such as mercaptans, formaldehyde, hydrocarbons and organic amines from gas streams and exhaust air are fixed.
  • the cleaning should be carried out up to residual concentrations of ⁇ 0.1 ppm of gaseous pollutants.
  • the regeneration should be effective and the lifetime long. Non-combustibility is also required.
  • the object of the invention is defined by the main claim use of a mineral granules, the naturally occurring smektitreiche clays / bentonites with a proportion of swellable Dreitechniksilikate of at least 50% by weight and / or naturally occurring nano-halloysites with a Halloysitanteil (7A or 10A type) of contains at least 50% by weight, dissolved as a gas adsorber for the removal of ozone, siloxanes, formaldehyde, mercaptans, hydrocarbons and organic amines from exhaust air / exhaust gas, natural gas, gaseous fuels and liquefied gas.
  • a mineral granules the naturally occurring smektitreiche clays / bentonites with a proportion of swellable Dreitechniksilikate of at least 50% by weight and / or naturally occurring nano-halloysites with a Halloysitanteil (7A or 10A type) of contains at least 50% by weight, dissolved as a
  • the mineral granules used according to the invention as gas adsorbers Nulate conventional processing methods (drying, preferably up to 50 ° C, breaking, fractionation, granulation, extrusion) and / - or a low-temperature plasma-technological treatment for surface modification of the adsorber granules are used.
  • the preparation can also be carried out by build-up granulation of powder material or spray drying.
  • the lifetime of the mineral granules used according to the invention as a gas adsorber in the filter system is long and the mineral granules are also not combustible.
  • the laden mineral granules used according to the invention as gas adsorbers can be reactivated by short-term injection of oxygen or air into the filter system in which they are contained as component.
  • the regeneration of clay minerals used according to the invention as a gas adsorber can also take place in an air-flow system in which low-temperature plasma is generated in the granule interstices and in the pores.
  • gases such as nitrogen or argon can be used in the plasma regeneration.
  • the regeneration can also take place in a continuously operating rotary adsorber.
  • the invention relates to the use of a mineral granulate or agglomerate comprising naturally occurring smectite-rich clays and / or bentonites with a proportion of swellable three-layer silicates of at least 50% by weight and / or naturally occurring nano-halloysites having a halide content (7A or 10A).
  • the mineral granulate or agglomerate has not been physically or chemically treated and is free from additives, as a gas adsorber for removing ozone, siloxanes, formaldehyde, mercaptans, hydrocarbons and organic amines from exhaust air, natural gas and gaseous fuels.
  • the swellable three-layer silicates have a specific surface area of 100 to 800 m 2 / g and a cation exchange capacity of at least 50 meq / 100g.
  • the smectite-rich clays / bentonites have a montmorillonite content of at least 75% by weight, advantageously of at least 50% by weight.
  • the hailoysites have a nanopore volume of up to 30%.
  • Fig. 1 The filter effect of bentonite granules
  • Fig. 2 A long-term measurement with Halloysitgranulat
  • Fig. 4 The filtering effect of halloysite at higher ozone concentration
  • Fig. 5 The desorption of methane from halloysite as a function of temperature
  • FIG. 6 The fixing of formaldehyde from waste air / waste gas streams to the mineral adsorber used according to the invention
  • FIGS. 7 to 10 The adsorption of dimethylamine on the mineral adsorber used according to the invention
  • the mineral granules used according to the invention as gas adsorbers for the removal of ozone are characterized in that naturally occurring mineral raw materials in granular form - without any additives and chemical treatments - are used.
  • the mineral granules used according to the invention preferably consist of natural ones Halloysites, bentonites or smektitrial clays and are prepared by drying to 50 ° C, breaking and fractionation. Particularly preferred for good gas permeability is the grain band 0.5 - 10 mm.
  • mineral granules with minimum contents of 7A and / or 10A-type halloysites of more than 50% by weight and / or swellable three-layer silicates of more than 50% by mass are used according to the invention as gas adsorbers.
  • the mineral granules used according to the invention as gas adsorbers serve as constituents / fillers of technical components and systems for the treatment / purification of, for example, ozone-containing gas and exhaust air streams. They eliminate both excess ozone and the maximum amount of ozone generated from ozone-forming processes, so that the natural ozone level in rooms is not exceeded.
  • the mineral granules used according to the invention as gas adsorbers for the removal of, for example, ozone are also characterized in that an energy input by means of low-temperature plasma takes place in granule clearances and pores of the adsorber.
  • a cartridge was used, which could be filled with various adsorbent materials.
  • On one side of the cartridge ozone-enriched air was flowed in and on the other side via a sensor the ozone concentration was measured.
  • the required ozone was generated with a laboratory ozonizer. In this a dielectrically impeded discharge is operated. Concentration measurements were made with a commercial instrument using the principle of UV absorption.
  • the materials were tested under conditions suitable for use in plasma technological processes.
  • the typical natural environmental exposure to ozone is in the range 0.02-0.05 ppm.
  • the samples were mixed with air and an ozone concentration of about one Magnitude (it was in the experiments (see Fig. 1 - 4) ozone concentrations of 0.25 ppm, 0.17 ppm, 0.16 ppm and 1.3 ppm set as initial values) higher, rinsed through.
  • ozone concentrations 0.25 ppm, 0.17 ppm, 0.16 ppm and 1.3 ppm set as initial values
  • FIG. 1 shows an example of the filter effect of bentonite.
  • the initial concentration of ozone was in the range of 0.25 ppm. Shown is the initial concentration of ozone and the effect on the passage of the ozone-enriched air stream through a cartridge with the filter granules bentonite (stratification 2.5 cm, diameter 5 cm).
  • the ozone concentration drops to about 0.03 ppm. This corresponds approximately to the ozone content in the experimental room.
  • FIG. 4 A test with a higher initial ozone concentration is shown in FIG. 4 for the adsorbent material Halloysite.
  • the measured ozone levels above the granules are in the same range as before measurements.
  • the device can also take the form of a be constructed of continuous rotary adsorber.
  • Sulfur compounds motor oil poison
  • a landfill gas was treated under the following conditions:
  • organosilicon Compounds: 10-20 mg / m 3
  • the service life of the selected mineral adsorber granulate was about 50 days for hydrogen sulfide and about 20 days for siloxanes, whereby with respect to siloxane a depletion of 10 to 30 times with respect to the raw gas contamination could be achieved.
  • HNT "Hailoysite Nanotubes"
  • the total sulfur content also includes the sulfur compounds (eg mercaptans) used for the odorization of industrial gases, with a reduction of 7 to 17 times the initial value during the test period compared with the total sulfur output concentration of 3.3 mg / m 3 has been.
  • sulfur compounds eg mercaptans
  • biogas was branched off in a bypass system in front of the engine of a combined heat and power plant and passed through a filter module.
  • the filter module consisted of three stacked filters, each with three chambers, each chamber having a volume of 5.301 dm 3 . With the help of a gas pump, the gas flow was evenly conducted over all filter columns. The filter columns were filled with halloysite.
  • FIG. 7 shows a comparison of the FTIR spectra of dimethylamine when passing through a bypass and the adsorbent P2, a bentonite, after 60 minutes. It can be seen that dimethylamine is adsorbed by P2.
  • FIG. 8 shows the associated time course of concentration of dimethylamine after flow through the mineral adsorbent P2. It is achieved a complete adsorption of the pollutant for the entire period considered.
  • FIG. 9 shows an example of the temporal concentration course of dimethylamine after flowing through the mineral adsorbent P5, a halloysite. In turn, a complete adsorption of the pollutant is achieved for the entire considered period.
  • FIG. 10 shows the time course of concentration of dimethylamine after flow through the mineral adsorbent P4, a zeolite. Again, a complete adsorption is observed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne l'utilisation d'un granulé ou agglomérat minéral, qui contient des argiles riches en smectite et à l'état naturel et/ou des bentonites ayant une certaine proportion de silicates à trois couches capables de gonfler et/ou des nano-halloysites à l'état naturel, le granulé ou agglomérat minéral n'ayant pas été traité chimiquement et étant exempt d'additifs, comme adsorbeur de gaz pour éliminer l'ozone, les siloxanes, le formaldéhyde, les mercaptans, les hydrocarbures et les amines organiques contenus dans de l'air sortant/des gaz d'échappement, du gaz naturel et des vecteurs énergétiques gazeux.
PCT/EP2011/001834 2010-04-12 2011-04-12 Utilisation de granulés minéraux naturels comme adsorbeurs de gaz pour l'élimination de composants toxiques gazeux Ceased WO2011128073A2 (fr)

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EP11719762A EP2558194A2 (fr) 2010-04-12 2011-04-12 Utilisation de granulés minéraux naturels comme adsorbeurs de gaz pour l'élimination de composants toxiques gazeux

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DE102010003880.6 2010-04-12
DE201010003880 DE102010003880A1 (de) 2010-04-12 2010-04-12 Mineralische Gasadsorber zur Beseitigung von Ozon aus Abluft/Abgas, Verfahren zu deren Herstellung und Regenerierung

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CN112023871A (zh) * 2020-08-28 2020-12-04 安徽同益净化科技有限公司 一种CO2扩散法制备纳米方解石VOCs吸附剂的方法
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